resumo
The uncovered potential of two safe dinuclear molybdenum complexes with non-rigid bidentate phosphinoyldithio formate ligands, each distinguished by their phosphorus atom substituents, was demonstrated for the first time in both the synthesis of poly(ethylene furan 2,5-dicarboxylate) (PEF) and its depolymerization. An in-depth evaluation of the reaction conditions, in terms of time and temperature, showcases the air and water stable handling of catalysts and their suitability to mediate PEF synthesis in a solvent-free, bulk polycondensation reaction, resulting in high efficiency and comparable properties as obtained with a benchmark titanium-based catalyst. Notably, excellent thermal properties and optically transparent polymers with over 89% transmittance in the visible region were achieved. Furthermore, these innovative molybdenum complexes were also able to efficiently prompt the chemical recycling of PEF through a glycolysis pathway under very mild conditions and in short reaction times. Two safe dinuclear Mo complexes with non-rigid bidentate phosphinoyldithio formate ligands, differing in phosphorus substituents, were demonstrated for the first time to enable both synthesis and recycling of PEF.
palavras-chave
PHOSPHINOYLDITHIOFORMATE LIGANDS; MECHANICAL-PROPERTIES; ACID; POLY(ETHYLENE-TEREPHTHALATE); POLYESTERS; COMPLEXES; TRANSPORT; DEGRADATION; MOBILITY; SORPTION
categoria
Chemistry; Science & Technology - Other Topics; Engineering
autores
Razinkov, D; Agostinho, B; Suman, SG; Sousa, AF
nossos autores
Andreia Fernandes de Sousa
Investigador Principal
Beatriz Agostinho
Estudante de doutoramentoProjectos
European network of FURan based chemicals and materials FOR a Sustainable development (FUR4Sustain)
CICECO - Aveiro Institute of Materials (UIDB/50011/2020)
CICECO - Aveiro Institute of Materials (UIDP/50011/2020)
Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)
agradecimentos
This work was supported by COST Action FUR4Sustain (CA18220) supported by COST (European Cooperation in Science and Technology). This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 (DOI 10.54499/UIDB/50011/2020), UIDP/50011/2020 (DOI 10.54499/UIDP/50011/2020) & LA/P/0006/2020 (DOI 10.54499/LA/P/0006/2020), financed by national funds through the FCT/MCTES (PIDDAC). The FCT is acknowledged for the research contract under Scientific Employment Stimulus to AFS (CEECIND/02322/2020 and DOI 10.54499/2020.02322.CEECIND/CP1589/CT0008) and for a doctorate grant to BA (2020.04495.BD). DR thanks for the STSM grant under the framework of COST Action CA18220, and DR and SGS acknowledge the Icelandic Centre of Research for support (grant no.173667). Ira Volkova is thanked for the illustration of the graphical abstract of this article.